6.

Module 2 Organic Chemistry

Alcohols

General formula alcohols CnH2n+1OH

Naming Alcohols
These have the ending -ol and if necessary the position
number for the OH group is added between the name stem
and the ol

OH

Butan-2-ol
CH3

CH

CH2

CH3
4

O
2-hydroxypropanoic acid

H3C CH C

If the compound has an OH group in addition to other

functional groups that need a suffix ending then the OH can be
named with the prefix hydroxy-):

OH

OH

Ethane-1,2-diol

HO CH2 CH2 OH
If there are two or more -OH groups then di, tri are used.
Add the e on to the stem name though

H2C

OH

HC

OH

H2C

OH

propane-1,2,3-triol

Bond angles in Alcohols

All the H-C-H bonds and CC-O are 109.5o (tetrahedral
shape), because there are 4
bond pairs of electrons
repelling to a position of
minimum repulsion.

109.5O

104.5O

The H-O- C bond is 104.5o (bent line

shape), because there are 2 bond
pairs of electrons and 2 lone pairs
repelling to a position of minimum
repulsion. Lone pairs repel more than
bond pairs so the bond angle is
reduced.

Different types of alcohols

H

H
O

H
H

Primary alcohols are alcohols

where 1 carbon is attached to
the carbon adjoining the
oxygen

H
H

Propan-1-ol
Primary

Propan-2-ol
Secondary
Secondary alcohols are alcohols
where 2 carbon are attached to
the carbon adjoining the oxygen

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methylpropan-2-ol
Tertiary
Tertiary alcohols are alcohols
where 3 carbon are attached to
the carbon adjoining the oxygen

1. Combustion of Alcohols
Alcohols combust with a clean flame

CH3CH2OH + 3O2

2CO2 + 3H2O

2. Reaction of Alcohols with Sodium

Observations:
effervescence,
the mixture gets hot,
sodium dissolves,
a white solid is produced.

Sodium reacts with alcohols

2CH3CH2O-Na+ + H2

2CH3CH2OH + 2Na

This reaction can be used as a test for alcohols

3. Substitution reactions of Alcohols to form Halogenoalkanes

Various halogenating compounds can be used to
substitute the OH group for a halogen

PCl5 / PCl3 / conc HCl / SOCl2 /

mixture of NaCl + H2SO4 can all be
uses for substituting a Cl

Reaction with phosphorous (V) halide

CH3CH2OH + PCl5

CH3CH2Cl + POCl3 + HCl

For Br and I it is best to use PI5, PI3

and Br equivalents. It is not suitable
to use NaBr, or NaI + H2SO4 to
produce HBr or HI because the
sulphuric acid with oxidise the
hydrogen halides to other products

This reaction with PCl5 (phosphorous(v)chloride) can be

used as a test for alcohols. You would observe misty
fumes of HCl produced.
Reaction with phosphorous (III) halide
PI3 + 3 CH3CH2OH

The phosphorous (III) halide can also be produced

in situ by reacting red phosphorus and the halogen.

3CH3CH2I + H3PO3

4. Oxidation reactions of the alcohols

The exact reaction, however, depends on
the type of alcohol, i.e. whether it is primary,
secondary, or tertiary, and on the
conditions.

Potassium dichromate K2Cr2O7 is an oxidising agent

that causes alcohols to oxidise.
Partial Oxidation of Primary Alcohols

Reaction: primary alcohol

aldehyde
Reagent: potassium dichromate (VI) solution and dilute
sulphuric acid.
Conditions: (use a limited amount of dichromate) warm
gently and distil out the aldehyde as it forms:

H
H

OH
CH3CH2CH2OH + [O]
propan-1-ol

An aldehydes name ends

in al
It always has the C=O bond
on the first carbon of the
chain so it does not need
an extra number

Ethanal

+ [O]

O
+ H2O

C
H

+ [O]

Observation: the
orange dichromate ion
(Cr2O72-) reduces to
the green Cr 3+ ion

+ H2O

CH3CH2CHO + H2O
propanal

Write the oxidation equations in a simplified form using [O] which represents O from the oxidising agent
When writing the formulae of aldehydes in a condensed way write CHO and not COH e.g.CH3CH2CHO

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Full Oxidation of Primary Alcohols

Reaction: primary alcohol
carboxylic acid
Reagent: potassium dichromate(VI) solution and dilute
sulphuric acid
Conditions: use an excess of dichromate, and heat
under reflux: (distill off product after the reaction
has finished)

Propanoic acid

OH

+ 2 [O]

O
+ H2O

C
O

OH

+ 2[O]

+ H2O

Observation: the
orange dichromate
ion (Cr2O72-) reduces
to the green Cr 3+ ion

O
CH3CH2CH2OH + 2[O]

CH3CH2COOH + H2O

propan-1-ol

Propanoic acid

Oxidation of Secondary Alcohols

Ketones end in -one

Reaction: secondary alcohol

ketone
Reagent: potassium dichromate(VI) solution and
dilute sulphuric acid.
Conditions: heat under reflux

When ketones have 5Cs

or more in a chain then it
needs a number to show
the position of the double
bond. E.g. pentan-2-one

Propanone
H

+ [O]

H
H

+ H2O

Observation: the
orange dichromate
ion (Cr2O72-) reduces
to the green Cr 3+ ion

Propanone

propan-2-ol

There is no further oxidation of the ketone under these conditions.

Tertiary alcohols cannot be oxidised at all by potassium dichromate: This is because there is no hydrogen
atom bonded to the carbon with the OH group
Distinguishing between Aldehydes and Ketones
The fact that aldehydes can be further oxidised to carboxylic acids whereas ketones cannot be further oxidised
is the chemical basis for tests that are commonly used to distinguish between aldehydes and ketones
Fehlings (Benedicts) solution
Reagent: Fehlings Solution containing blue Cu 2+ ions.
Conditions: heat gently
Reaction: aldehydes only are oxidised by Fehlings solution into a carboxylic
acid and the copper ions are reduced to copper(I) oxide
Observation: Aldehydes :Blue Cu 2+ ions in solution change to a red
precipitate of Cu2O. Ketones do not react

CH3CHO + 2Cu2+ + 2H2O

The presence of a carboxylic acid

can be tested by addition of
sodium carbonate. It will fizz and
produce carbon dioxide

CH3COOH + Cu2O + 4H+

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Organic techniques
Distillation
thermometer

In general used as separation technique to separate an

organic product from its reacting mixture. Need to
collect the distillate of the approximate boiling point
range of the desired liquid.
Classic AS reaction using distillation
Reaction: primary alcohol
aldehyde
Reagent: potassium dichromate (VI) solution and dilute
sulphuric acid.
Conditions: use a limited amount of dichromate and
warm gently and distil out the aldehyde as it forms
[This prevents further oxidation to the carboxylic acid]
Observation
Orange dichromate solution changes to green colour of
Cr3+ ions

Liebig condenser

Water
out
Water in
Heat

Note the bulb of the thermometer should be at the

T junction connecting to the condenser to
measure the correct boiling point
Note the water goes in the bottom of the condenser to go
against gravity. This allows more efficient cooling and
prevents back flow of water.

Reflux
Reflux is used when heating organic reaction mixtures for long
periods. The condenser prevents organic vapours from escaping
by condensing them back to liquids.
Never seal the end of the condenser as the build up of gas
pressure could cause the apparatus to explode. This is true of any
apparatus where volatile liquids are heated including the distillation
set up

Classic AS reaction using reflux

Reaction: primary alcohol
carboxylic acid
Reagent: potassium dichromate(VI) solution and dilute
sulphuric acid
Conditions: use an excess of dichromate, and heat
under reflux: (distill off product after the reaction
has finished using distillation set up)
CH3CH2CH2OH + 2[O]
CH3CH2CO2H + H2O
Observation
Orange dichromate solution changes to green colour of
Cr3+ ions

Anti-bumping granules are added to the flask in both distillation and reflux to prevent vigorous, uneven
boiling.

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Purifying an organic liquid

Put the distillate of impure product into a separating funnel

wash product by adding either

sodium hydrogencarbonate solution , shaking and
releasing the pressure from CO2 produced.
Saturated sodium chloride solution

Sodium hydrogencarbonate will

neutralise any remaining reactant acid.
Sodium chloride will help separate the
organic layer from the aqueous layer

Allow the layers to separate in the funnel, and then run and
discard the aqueous layer.
Run the organic layer into a clean, dry conical flask and add
three spatula loads of drying agent (anhydrous sodium
sulphate) to dry the organic liquid.

The drying agent should

be insoluble in the organic liquid
not react with the organic liquid

Carefully decant the liquid into the distillation flask

Distill to collect pure product
Separating funnel

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Halogenoalkanes
Naming Halogenoalkanes

Br

Based on original alkane, with a prefix indicating halogen atom:

Fluoro for F; Chloro for Cl; Bromo for Br; Iodo for I.

H
H

Cl

Substituents are listed alphabetically

1-bromopropane

Classifying Halogenoalkanes

2-chloro-2-methylbutane

Halogenoalkanes can be classified as primary, secondary or tertiary depending

on the number of carbon atoms attached to the C-X functional group.
H

Br

Br

Primary halogenoalkane
One carbon attached to the
carbon atom adjoining the
halogen

Secondary halogenoalkane
Two carbons attached to the
carbon atom adjoining the
halogen

Cl

Tertiary halogenoalkane
Three carbons attached to the
carbon atom adjoining the
halogen

Halogenoalkanes undergo either

substitution or elimination reactions

Reactions of Halogenoalkanes
Nucleophilic substitution reactions

Substitution: swapping a halogen atom for another atom or groups of atoms

Nucleophile: electron pair donator e.g. :OH-, :NH3, CN:Nu represents any nucleophile they
always have a lone pair and act as
electron pair donators

The Mechanism: We draw (or outline) mechanisms to

show in detail how a reaction proceeds
Nu:-

The nucleophiles
attack the positive
carbon atom

Nu + X-

We use curly arrows in mechanisms (with

two line heads) to show the movement of
two electrons

A curly arrow will always start

from a lone pair of electrons or
the centre of a bond

The rate of these substitution reactions depends on the strength

of the C-X bond
The weaker the bond, the easier it is to break and the faster the reaction.
The iodoalkanes are the fastest to substitute and the
fluoroalkanes are the slowest. The strength of the C-F bond is
such that fluoroalkanes are very unreactive

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The carbon has a small

positive charge because
of the electronegativity
difference between the
carbon and the halogen

Bond enthalpy /
kJmol-1
C-I

238

C-Br

276

C-Cl

338

C-F

484

Comparing the rate of hydrolysis reactions

Hydrolysis is defined as the splitting of a molecule ( in this
case a halogenoalkane) by a reaction with water

Water is a poor nucleophile but it can

react slowly with halogenoalkanes in a
substitution reaction

CH3CH2OH + X- + H+

CH3CH2X + H2O

Aqueous silver nitrate is added to a halogenoalkane and the

halide leaving group combines with a silver ion to form a
SILVER HALIDE PRECIPITATE.
The precipitate only forms when the halide ion has left the
halogenoalkane and so the rate of formation of the precipitate
can be used to compare the reactivity of the different
halogenoalkanes.

CH3CH2I + H2O

CH3CH2OH + I- + H+

Ag+ (aq) + I-(aq)

AgI (s) - yellow precipitate

The quicker the precipitate is formed, the faster the

substitution reaction and the more reactive the haloalkane

AgI (s) - yellow precipitate

AgBr(s) cream precipitate
AgCl(s) white precipitate

The iodoalkane forms a precipitate with

the silver nitrate first as the C-I bond is
weakest and so it hydrolyses the quickest

The rate of these substitution reactions depends on the strength

of the C-X bond . The weaker the bond, the easier it is to break
and the faster the reaction.

forms faster

Nucleophilic substitution with aqueous hydroxide ions

Change in functional group: halogenoalkane
alcohol
Reagent: potassium (or sodium) hydroxide
Conditions: In aqueous solution; Heat under reflux
Mechanism:Nucleophilic Substitution
Role of reagent: Nucleophile, OH-

Br

+ KOH

1-bromopropane

The OH is a stronger nucleophile than water as it has a full negative

charge and so is more strongly attracted to the C+

OH

+ KBr

propan-1-ol

The aqueous conditions needed

is an important point. If the
solvent is changed to ethanol an
elimination reaction occurs

SN2 nucleophilic substitution mechanism for halogenoalkanes

H
H3C
-HO:

C
H

CH3 H
Br

HO

Br

H3C

OH + :Br -

transition state.
This mechanism occurs with primary halogenoalkanes

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SN1 nucleophilic substitution mechanism for tertiary halogenoalkanes

Tertiary haloalkanes undergo nucleophilic substitution in a different way

CH3

CH3
H3C C

H3C C

Br

H3C C

:OH-

The Br first breaks

away from the
haloalkane to form
a carbocation
intermediate

OH

CH3

CH3

CH3

Tertiary halogenoalkanes
undergo this mechanism as the
tertiary carbocation is made
stabilised by the electron
releasing methyl groups around it.
(see alkenes topic for another
example of this).
Also the bulky methyl groups
prevent the hydroxide ion from
attacking the halogenoalkane in
the same way as the mechanism
above

CH3

The hydroxide
nucleophile then
attacks the positive
carbon

Primary halogenoalkanes dont do the SN1 mechanism because they would only form an unstable primary
carbocation.

Nucleophilic substitution with ammonia

Change in functional group: halogenoalkane
amine
Reagent: NH3 dissolved in ethanol
Conditions: Heating under pressure in a sealed
tube
Mechanism: Nucleophilic Substitution
Type of reagent: Nucleophile, :NH3

Br

+ 2NH3

NH2

+ NH4Br

propylamine
Naming amines:

CH3 CH2 C

H
+
CH3 CH2 C
3HN:
H

Br

In the above example

propylamine, the propyl shows
the 3 Cs of the carbon chain.

:Br -

Sometimes it is easier to use the

IUPAC naming for amines e.g.
Propan-1-amine

:NH3

H
CH3 CH2 C

NH2

+ NH4Br

H
Further substitution reactions can occur between the haloalkane and the amines
formed leading to a lower yield of the amine. Using excess ammonia helps
minimise this.

Further reactions

N:
H

RX

RX
H

H
N:
R

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RX

N:
R

N:
R

Elimination reaction of halogenoalkanes

Elimination: removal of small molecule

(often water) from the organic molecule

Elimination with alcoholic hydroxide ions

Change in functional group: halogenoalkane
alkene
Reagents:
Potassium (or sodium) hydroxide
Conditions:
In ethanol ; Heat
Mechanism:
Elimination
Role of reagent: Base, OH-

Br

+ KOH

1-bromopropane

+ KBr + H2O

propene

Note the importance of the solvent to the type of reaction here.

Aqueous: substitution
Alcoholic: elimination
Often a mixture of products from both elimination and substitution occurs

With unsymmetrical secondary

and tertiary halogenoalkanes
two (or sometimes three)
different structural isomers can
be formed

2-methyl -2chlorobutane can give

2-methylbut-1-ene and
2-methylbut-2-ene

H
H

C
C

H
C

H
H
C

Cl

H
H
H

C
H

C
C

The structure of the halogenoalkane also has an effect on the

degree to which substitution or elimination occurs in this reaction.
Primary tends towards substitution
Tertiary tends towards elimination

Uses of halogenoalkanes
Haloalkanes have been used as refrigerants, fire retardants, pesticides and aerosol propellants
chloroalkanes and chlorofluoroalkanes can be used as solvents
CH3CCl3 was used as the solvent in dry cleaning

Some halogenoalkanes
have low flammability

Many of these uses have now been stopped due to the toxicity of
halogenoalkanes and also their detrimental effect on the ozone
layer

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